Edge-cladding glass of disc laser glass

ABSTRACT

A glass for edge-cladding a disc laser glass, comprising, in mol%, followed in parentheses by wt % value, P2O5 46- 63,  (64-76)   Al2O3 4- 8,  (3.5-7.5)  B2O3 0- 5,   (0-3.0) K2O 2- 20, (2.5-16.5) Na2O 0- 15,  (0-8.5) Li2O 0- 14,  (0-3.5) K2O + Na2O + Li2O 18- 30, (11.5-20.5)  CuO 2- 20, (1.4-13.5) ZnO 0- 15,  (0-11.5) MgO 0- 5, (0-2.0)   and CuO + ZnO + MgO 7- 20. (4.7-13.5).

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to an edge-cladding glass for a disc laser glass. More particularly, it relates to an edge-cladding glass for a disc laser glass, which has a low fusion temperature, a high thermal expansion coefficient and a high absorption coefficient in the vicinity of the central wavelength of laser light.

2. Description of the Prior Art

It is known that when spontaneous emission light generated in a disc laser glass in which energy has been accumulated by the pumping of a Xe flash lamp is reflected and scattered at disc edges and amplified such that the gain exceeds the loss; oscillation, known as parasitic oscillation, occurs. When oscillation occurs, the energy accumulated is consumed instantaneously. This phenomenon can be prevented by surrounding the circumferencial portion of the disc with a medium having reduced reflection and scattering and capable of absorbing the laser light (e.g., the glass of this invention) so that the spontaneous emission light cannot be reflected and scattered at disc edges. This contrivance is known in the art as "edge cladding" and is discribed in U.S. Pat. Nos. 3,885,974 and 3,966,448.

A general method of edge-cladding comprises mixing a low fusion temperature glass powder with a dispersing agent to form a slurry, coating the slurry on the edge of the disc laser glass, and heat-treating the coated glass at a temperature below the temperature at which the disc glass is softened and deformed, to thereby melt-bond the low fusion temperature glass to the edge of the disc glass. This method tends to leave a number of bubbles in the clad glass, which increase considerably the reflection and scattering of spontaneous emission light.

SUMMARY OF THE INVENTION

An object of this invention is to provide a glass for edge-cladding having a low fusion temperature, a high expansion co-efficient, and a high absorption coefficient in the vicinity of the central wavelength (1.051 to 1.054μ, particularly 1.052μ) of laser light.

When a disc glass is edge-cladded with the glass of this invention, residual bubbles are reduced, and the reflection and scattering of spontaneous emission light can be maintained low.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING

The FIGURE shows a state of reflection and scattering of a glass on which the edge-cladding glass of this invention has been coated.

DETAILED DESCRIPTION OF THE INVENTION

The disc glass to which the edge-cladding glass of this invention is applied is a fluorophosphate glass which has a coefficient α of thermal expansion ranging about 145×10⁻⁷ to about 175×10⁻⁷ /°C. (100°-200° C.), a transition point Tg ranging about 380° to about 450° C., and a refractive index [nd] ranging from about 1.44 to about 1.48. Such a glass is described in U.S. Patent application Ser. No. 819,440 filed July 27, 1977 issued Oct. 17, 1978, as U.S. Pat. No. 4,120,814.

The edge-cladding glass of this invention comprises, in mol%, followed in parentheses by wt% value,

    ______________________________________                                         P.sub.2 O.sub.5    46- 63,  (64-76)                                            Al.sub.2 O.sub.3   4- 8,    (3.5-7.5)                                          B.sub.2 O.sub.3    0- 5,     (0-3.0)                                           K.sub.2 O          2- 20,   (2.5-16.5)                                         Na.sub.2 O         0- 15,    (0-8.5)                                           Li.sub.2 O         0- 14,    (0-3.5)                                           K.sub.2 O + Na.sub.2 O + Li.sub.2 O                                                               18- 30,  (11.5-20.5)                                        CuO                2- 20,   (1.4-13.5)                                         ZnO                0- 15,    (0-11.5)                                          MgO                0- 5,     (0-2.0)                                                                       and                                                CuO + ZnO + MgO    7- 20.   (4.7-13.5).                                        ______________________________________                                    

P₂ O₅ the main component of the glass, decreases the softening point of the edge-cladding glass. If the amount of P₂ O₅ is 46 mol% or less, the edge-cladding glass tends to devitrify. If the amount of P₂ O₅ is 63 mol% or more, residual bubbles increase after fusion process.

Al₂ O₃ is required in an amount of 4 mol% or more to improve the devitrification resistance and chemical durability of the edge-cladding glass. When the amount of Al₂ O₃ exceeds 8 mol%, the edge-cladding glass has a high softening point.

B₂ O₃ is effective to increase the devitrification resistance of the edge-cladding glass. The effect of B₂ O₃ does not increase even when the amount of B₂ O₃ exceeds 5 mol%, but rather the softening point of the edge-cladding glass increases. Accordingly B₂ O₃ is used in amounts up to 5 mol% such that the softening point for the edge-cladding glass is below the temperature at which the disc glass is softened.

The alkali metal oxides are essential to decrease the softening point of the edge-cladding glass and to increase the coefficient of thermal expansion of the edge-cladding glass. The total amount of K₂ O+Na₂ O+Li₂ O must be 18 mol% or more, but if the total amount exceeds 30 mol%, the edge-cladding glass tends to devitrify.

K₂ O improves the devitrification resistance of the edge-cladding glass, and is required in an amount of 2 mol% or more. The K₂ O is also the most effective component to increase the coefficient of thermal expansion of the edge-cladding glass. The suitable upper limit on the amount of K₂ O is 20 mol% because K₂ O gives the highest softening point among the alkali metal oxides and the chemical durability thereof is low.

Na₂ O and Li₂ O, which can replace a portion of K₂ O, are effective to adjust the coefficient of thermal expansion of the edge-cladding glass to that of the disc glass. Since Na₂ O and Li₂ O give lower softening points than that of K₂ O, they are used in an amount of 0 to 15 mol%, and 0 to 14 mol%, respectively.

CuO has a high absorption in a wavelength region of 0.7 to 1.3μ, and is essential to absorb laser light. The amount of CuO must be 2 mol% or more so that the edge-cladding glass has a sufficient absorption at an ordinary thickness e.g., about 0.2 to 1.0 mm. Since CuO gives a relatively low softening point and tends to reduce residual bubbles after fusion process, such can be incorporated effectively in a considerable amount. The effect however scarcely changes when the amount of CuO exceeds 20 mol%.

ZnO gives a relatively low softening point and exhibits properties similar to CuO, as such ZnO can replace a portion of CuO. In particular, a glass having a high CuO content tends to undergo thermal damage by a Xe flash lamp. In such a case, ZnO is an effective substitute for CuO. The suitable upper limit of the amount of ZnO is 15 mol% because ZnO tends to increase residual bubbles and the use thereof in too large amount increases reflection and scattering of laser light.

Similar to ZnO, MgO can be used in place of a portion of CuO. The suitable amount of MgO is 5 mol% or less because MgO increases the softening point of the edge-cladding glass.

The total amount of CuO+ZnO+MgO should be 7 to 20 mol% so as to retain the chemical durability of the edge-cladding glass.

Edge-cladding glasses in accordance with the present invention preferably have a fusion temperature of about 400° to 480° C., an expansion coefficient of about 130×10⁻⁷ to 170×10⁻⁷ /°C., and the coefficient of adsorption preferably ranges from 20 to 250 cm⁻¹.

Examples of the glass of this invention along with their thermal properties, absorption coefficients at 1.052μ [k₁.052 (cm⁻¹)] and the magnitude R(%) of reflection and scattering after fusion process are shown below. Each component is shown by mol% and (in parentheses below the mol% value) in wt%.

                                      EXAMPLES                                     __________________________________________________________________________                Example No.                                                                    1   2   3   4   5   6   7   8                                       __________________________________________________________________________     P.sub.2 O.sub.5                                                                           49.29                                                                              62.42                                                                              51.43                                                                              51.43                                                                              53.06                                                                              55.71                                                                              57.42                                                                              54.69                                              (64.85)                                                                            (76.00)                                                                            (65.88)                                                                            (65.77)                                                                            (67.47)                                                                            (68.68)                                                                            (69.62)                                                                            (69.00)                                 Al.sub.2 O.sub.3                                                                          6.10                                                                               5.56                                                                               4.43                                                                               4.43                                                                               6.63                                                                               6.96                                                                               7.17                                                                               7.81                                               (5.76)                                                                             (4.86)                                                                             (4.08)                                                                             (4.08)                                                                             (6.06)                                                                             (6.16)                                                                             (6.25)                                                                             (7.08)                                  B.sub.2 O.sub.3                                                                           2.05                                                                               2.60                                                                               2.14                                                                               2.14                                                                               2.21                                                                               2.32                                                                               2.39                                                                               --                                                 (1.32)                                                                             (1.55)                                                                             (1.34)                                                                             (1.34)                                                                             (1.38)                                                                             (1.40)                                                                             (1.42)                                                                             (--)                                    CuO        15  7   12  2   4.76                                                                               5   15  15                                                 (11.06)                                                                            (4.78)                                                                             (8.61)                                                                             (1.43)                                                                             (3.39)                                                                             (3.45)                                                                             (10.19)                                                                            (10.60)                                 K.sub.2 O  11.78                                                                              9.60                                                                               12.50                                                                              12.50                                                                              14.29                                                                              13.5                                                                               10.8                                                                               9.64                                               (10.28)                                                                            (7.76)                                                                             (10.63)                                                                            (10.61)                                                                            (12.06)                                                                            (11.04)                                                                            (8.69)                                                                             (8.07)                                  Na.sub.2 O 7.89                                                                               6.41                                                                               8.33                                                                               8.33                                                                               14.29                                                                              9   7.22                                                                               6.43                                               (4.53)                                                                             (3.41)                                                                             (4.65)                                                                             (4.65)                                                                             (7.93)                                                                             (4.84)                                                                             (3.82)                                                                             (3.54)                                  Li.sub.2 O 7.89                                                                               6.41                                                                               4.17                                                                               4.17            6.43                                               (2.18)                                                                             (1.64)                                                                             (1.12)                                                                             (1.12)                                                                             (--)                                                                               (--)                                                                               (--)                                                                               (1.71)                                  ZnO                5   15      5                                                          (--)                                                                               (--)                                                                               (3.67)                                                                             (11.00)                                                                            (--)                                                                               (3.53)                                                                             (--)                                                                               (--)                                    MgO                        4.76                                                                               2.51                                                       (--)                                                                               (--)                                                                               (--)                                                                               (--)                                                                               (1.72)                                                                             (0.88)                                                                             (--)                                                                               (--)                                    Tg (°C.)                                                                           356 340 333 326 366 379 378 374                                     Sp (°C.)                                                                           395 385 373 367 407 423 421 416                                     α(10.sup.-7 /°C.)                                                            152 147 155 158 160 163 150 141                                     k.sub.1.052 (cm.sup.-1)                                                                   180 84  144 25  57  60  180 180                                     R (%)      0.09                                                                               0.14                                                                               0.15                                                                               0.19                                                                               0.15                                                                               0.18                                                                               0.17                                                                               0.17                                    CuO + ZnO + MgO                                                                           (11.06)                                                                            (4.78)                                                                             (12.28)                                                                            (12.43)                                                                            (5.11)                                                                             (7.86)                                                                             (10.19)                                                                            (10.60)                                 K.sub.2 O + Na.sub.2 O +                                                       LiO        (16.99)                                                                            (12.81)                                                                            (16.4)                                                                             (16.38)                                                                            (19.99)                                                                            (15.86)                                                                            (12.51)                                                                            (13.32)                                 __________________________________________________________________________                Example No.                                                                    9   10  11  12  13  14  15                                          __________________________________________________________________________     P.sub.2 O.sub.5                                                                           52.46                                                                              55.71                                                                              56.71                                                                              56.71                                                                              55.71                                                                              53.57                                                                              55.71                                                  (67.59)                                                                            (70.11)                                                                            (73.72)                                                                            (74.15)                                                                            (66.70)                                                                            (67.46)                                                                            (68.18)                                     Al.sub.2 O.sub.3                                                                          5.58                                                                               4.96                                                                               5.96                                                                               5.96                                                                               6.96                                                                               6.70                                                                               6.96                                                   (5.16)                                                                             (4.48)                                                                             (5.56)                                                                             (5.60)                                                                             (5.99)                                                                             (6.06)                                                                             (6.12)                                      B.sub.2 O.sub.3                                                                           4.46                                                                               0.32                                                                               2.32                                                                               2.33                                                                               2.32                                                                               2.23                                                                               2.32                                                   (2.82)                                                                             (0.20)                                                                             (1.48)                                                                             (1.49)                                                                             (1.36)                                                                             (1.38)                                                                             (1.39)                                      CuO        15  19  7   7   15  15  15                                                     (10.83)                                                                            (13.40)                                                                            (5.10)                                                                             (5.13)                                                                             (10.06)                                                                            (10.58)                                                                            (10.29)                                     K.sub.2 O  9.64                                                                               8.57                                                                               5.33                                                                               3.0 20  7.5 12                                                     (8.24)                                                                             (7.16)                                                                             (4.60)                                                                             (2.60)                                                                             (15.89)                                                                            (6.27)                                                                             (9.75)                                      Na.sub.2 O 6.43                                                                               5.72                                                                               11.34                                                                              14.0    15  8                                                      (3.62)                                                                             (3.14)                                                                             (6.44)                                                                             (7.99)                                                                             (--)                                                                               (8.25)                                                                             (4.28)                                      Li.sub.2 O 6.43                                                                               5.72                                                                               11.34                                                                              11.0                                                               (1.74)                                                                             (1.52)                                                                             (3.10)                                                                             (3.03)                                                                             (--)                                                                               (--)                                                                               (--)                                        ZnO                                                                            MgO                                                                            Tg (°C.)                                                                           358 353 328 323 383 385 371                                         Sp (°C.)                                                                           406 394 373 369 429 419 416                                         α(10.sup.-7 /°C.)                                                            146 145 151 160 150 144 140                                         k.sub.1.052 (cm.sup.-1)                                                                   180 228 84  84  180 180 180                                         R (%)      0.18                                                                               0.16                                                                               0.10                                                                               0.12                                                                               0.22                                                                               0.19                                                                               0.12                                        CuO + ZnO + MgO                                                                           (10.83)                                                                            (13.40)                                                                            (5.10)                                                                             (5.13)                                                                             (10.06)                                                                            (10.58)                                                                            (10.29)                                     K.sub.2 O + Na.sub.2 O +                                                       LiO        (13.6)                                                                             (11.82)                                                                            (14.14)                                                                            (13.62)                                                                            (15.89)                                                                            (14.52)                                                                            (14.03)                                     __________________________________________________________________________

The magnitude of reflection and scattering is measured as illustrated in the accompanying drawing. That is, light ray is emitted from the side of the disc glass against the interface between the disc glass and the cladding glass at an angle of incidence of 45°. The light ray is partly reflected at the interface, and the remainder advances through the cladding glass and is absorbed there. When bubbles are present inside the cladding glass, the light ray scattered by the bubbles is not completely absorbed, but reflected. This results in a reflecting of light rays in random directions with regard to an angle of incidence of 45°.

On the other hand, if there is no cladding glass, the light which falls upon the glass at an angle of incidence of 45° will be totally reflected at the interface between the cladding glass and the air.

Where the intensity of this reflecting light is represented by I_(o) and the intensity of the above-described reflected and scattered light is represented by I, the magnitude is calculated by R(%)=I/I_(o) ×100.

In the edge-cladding glass of this invention, the alkali metal oxides can be replaced by the alkali metal fluorides. Since flourine mostly volatilizes during melting and scarcely remains in the glass, the fluorine does not greatly affect the various properties of the edge-cladding glass.

When the alkali metal oxides of the glass of Example 15 are changed to alkali metal fluorides, the properties of the resulting glass are as follows:

    ______________________________________                                         Tg (°C.)                                                                        Sp (°C.)                                                                         α(10.sup.-7 /°C.)                                                             k.sub.1.052 (cm.sup.-1)                                                                 R (%)                                    ______________________________________                                         370     422      142         180      0.155                                    ______________________________________                                    

As starting materials for the edge-cladding glass of this invention phosphoric anhydride, ortho-phosphoric acid, alumina, aluminum hydroxide, boric anhydride, boric acid, copper oxide, potassium carbonate, sodium carbonte, lithium carbonate, potassium fluoride, sodium fluoride, lithium fluoride, zinc oxide, and magnesium carbonate are useful. By mixing the starting materials in the appropriate amounts and melting at about 1,100° to about 1,200° C. in a crucible the edge-cladding glass of this invention can be produced.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and the scope thereof. 

What is claimed is:
 1. A glass for edge-cladding a disc laser glass, consisting essentially of, in mol%,

    ______________________________________                                         P.sub.2 O.sub.5   46-63,                                                       Al.sub.2 O.sub.3   4-8,                                                        B.sub.2 O.sub.3    0-5,                                                        K.sub.2 O          2-20,                                                       Na.sub.2 O         1-15,                                                       Li.sub.2 O         0-14,                                                       K.sub.2 O + Na.sub.2 O + Li.sub.2 O                                                              18-30,                                                       CuO                2-20,                                                       ZnO                0-15,                                                       MgO                0-5, and                                                    CuO + ZnO + MgO    7-20.                                                       ______________________________________                                    


2. An edge-clad disc laser glass comprising a disc glass having a coefficient α of thermal expansion ranging about 145×10⁻⁷ to about 175×10⁻⁷ /°C. (100°-200° C.), a transition point Tg ranging about 380° to about 450° C., and a refractive index (nd) ranging from about 1.44 to about 1.48, the circumferential portion of which is surrounded by a medium having reduced reflection and scattering and capable of absorbing laser light, consisting essentially of, in mol%:

    ______________________________________                                         P.sub.2 O.sub.5   46-63,                                                       Al.sub.2 O.sub.3   4-8,                                                        B.sub.2 O.sub.3    0-5,                                                        K.sub.2 O          2-20,                                                       Na.sub.2 O         1-15,                                                       Li.sub.2 O         0-14,                                                       K.sub.2 O + Na.sub.2 O + Li.sub.2 O                                                              18-30,                                                       CuO                2-20,                                                       ZnO                0-15,                                                       MgO                0-5, and                                                    CuO + ZnO + MgO    7-20.                                                       ______________________________________                                     